Lead-lead oxide-carbon nanocomposite for energy storage cells and method of preparation

ABSTRACT

Lead/lead oxide/carbon (“Pb—O—C”) nanocomposite materials are useful as electrode active materials for electrodes in lithium and sodium batteries. A Pb—O—C nanocomposite as described herein comprises Pb and lead oxide nanoparticles homogeneously dispersed in a carbon nanoparticle matrix. In the nanocomposite, the other element or elements (e.g., transition metals, Al, Si, P, Sn, Sb, and Bi) can be alloyed with the Pb nanoparticles, incorporated as a mixed oxide with the lead oxide nanoparticles, or can be present as distinct elemental or oxide nanoparticles within the carbon nanoparticle matrix. In some embodiments, the additional element or elements are present as alloys and mixed oxides with the Pb materials and as distinct elemental and/or oxide nanoparticles. In a preferred embodiment the Pb nanoparticles surface is oxidized to lead oxide thus creating a shell on core nanostructure.

CONTRACTUAL ORIGIN OF THE INVENTION

The United States Government has rights in this invention pursuant toContract No. DE-AC02-06CH11357 between the United States Government andUChicago Argonne, LLC representing Argonne National Laboratory.

FIELD OF THE INVENTION

This invention relates to nanocomposite materials comprising lead,oxygen, and carbon. More particularly, this invention relates tonanocomposite materials comprising nanoparticles of metallic lead andlead oxide dispersed in a matrix of carbon nanoparticles, e.g.,nanoparticles in which the metallic lead is surrounded by a shell oflead oxide, and to a method of preparing such nanocomposite materials.

BACKGROUND

Advanced Li-ion and Na-ion batteries that can deliver high energies andcapacities require new high-performance anodes. Anode materials thatundergo alloying and conversion-type electrochemical reactions have beenstudied as alternative electrodes to graphite and hard carbon with thepromise of higher capacities, and potentially higher energy densities.Lead (Pb) and lead oxides (“PbOx”, e.g., PbO, PbO₂, Pb₃O₄, and mixturesthereof) have potential advantages of low cost and high volumetricenergy density for rechargeable battery applications.

In fact when the Argonne BATPAC model (see theanl(dot)gov/cse/batpac-model-software website page) is used with Pb asanode, and layered sodium transition metal oxide as cathode thecalculated energy density for a sodium-ion pouch cell design is 549Wh/L, and the cost is projected quite low at 63.5 USD/kWh. These metricsare certainly competitive with many grid storage battery systems;however, lead toxicity is a concern. On the plus side, Pb is one of themost recycled materials in the world, with a high recycling rate closeto 99% in the United States. With the rapid progress of in-line lithium-and sodium-ion battery recycling technologies, lead-based materialscould become a viable contender for high-energy, low-cost anodes in thefuture if the performance can be improved and validated.

Another major concern with lead-based anodes (Pb anodes), however, ispoor cycle stability due to large volume expansion and contractionduring the alloying and conversion reactions. This problem has generallylimited practical application of such Pb anode materials. For example,conventional Pb and PbOx electrodes show rapid capacity decay in lithiumand sodium cells. Because of these problems, there is an ongoing needfor new Pb and PbOx electrode materials. The materials and methodsdescribed herein address this need.

SUMMARY

Lead/lead oxide/carbon (“Pb—O—C”) nanocomposite materials are describedherein. The nanocomposites are useful as electrode active materials forelectrodes (e.g., anodes) in lithium-ion and sodium-ion secondaryelectrochemical cells and batteries (also referred to herein forconvenience as “lithium cells” and “sodium cells”). A Pb—O—Cnanocomposite as described herein comprises Pb and PbOx nanoparticlesand/or cores of lead (Pb) encapsulated in lead-oxide (PbOx) shells (alsoreferred to as “shell on core PbOx@Pb”), homogeneously dispersed in acarbon nanoparticle matrix. Optionally, one or more other elements canbe incorporated in the nanocomposite. The other element or elements(e.g., transition metals, Al, Si, P, Sn, Sb, and Bi) can be alloyed withthe Pb nanoparticles, incorporated as a mixed oxide with the PbOxnanoparticles, or can be present as distinct elemental or oxidenanoparticles within the carbon nanoparticle matrix. In someembodiments, the additional element or elements are present as alloysand mixed oxides with the Pb materials and as distinct elemental and/oroxide nanoparticles.

The nanocomposites can be prepared by a high-energy ball millingprocess. The process comprises grinding a mixture of a lead oxidematerial (e.g., PbO, PbO₂, Pb₃O₄, and the like) and a carbon material(e.g., carbon black, hard carbon, or graphite) together in a high-energyball mill loaded at room temperature, under an inert atmosphere. Duringhigh-energy ball milling, PbOx reacts with carbon to undergo a redoxreaction producing elemental Pb and carbon dioxide. The energy providedby the milling and vibration is great enough to induce thereduction-oxidation reaction. The ball milling is continued until thestarting lead oxide and carbon materials are pulverized a homogeneousdispersion of the resulting Pb nanoparticles and PbOx nanoparticleswithin a matrix of carbon nanoparticles forms. Typically, this processcan take several hours (e.g., 1 to 12 hours). Optionally, heat-treatmentat a temperature of about 30° C. to about 200° C. in air can be appliedto the ball-milled product to form a PbOx passive layer on the surfaceof the Pb nanoparticles. In this manner, a PbOx@Pb shell on corenanoparticle is formed.

One or more additional element can be incorporated in the nanocompositeby combining a material comprising the other element or elements (e.g.,an element or elements such as transition metals, Al, Si, P, Sn, Sb, andBi) with the PbOx and carbon materials during the grinding process. Insuch cases, these materials may also be referred to herein as Pb—O—Cnanocomposites or as Pb_(y)M_(1−y)-O—C nanocomposites, where M refers tothe one or more additional elements included in the material, and 0<y<1,more typically 0.5<y<1, and preferably 0.5<y<0.8. The other materialscan be added in elemental form, as an oxide, as a salt, or in any otherform, and then can undergo redox reactions with the carbon and/or PbOx,and or alloying reactions with the Pb, depending on whether the materialcontaining the element or elements are reactive with lead, carbon,and/or PbOx under the high-energy ball milling conditions.

Electrochemical data for Pb—O—C and Pb_(y)M_(1−y)-O—C nanocompositesdescribed herein in lithium and sodium cells show higher reversiblecapacity and improved cycle stability compared to previously reporteddata for conventional lead and lead oxide materials.

The following non-limiting embodiments of the methods described hereinare provided below to illustrate certain aspects and features of thecompositions and methods described herein.

Embodiment 1 is a lead-lead oxide-carbon (Pb—O—C) nanocompositecomprising nanoparticles of lead (Pb) and nanoparticles of a lead oxide(PbOx) homogeneously dispersed in a carbon nanoparticle matrix.

Embodiment 2 comprises the nanocomposite of embodiment 1, wherein thenanoparticles of Pb have a mean diameter of about 2 to about 20 nm asdetermined by electron microscopy.

Embodiment 3 comprises the nanocomposite of embodiment 1 or 2, whereinnanoparticles of the PbOx have a mean diameter of about 2 to about 20 nmas determined by electron microscopy.

Embodiment 4 comprises the nanocomposite of any one of embodiments 1 to3, wherein the nanocomposite has a Pb:C elemental ratio of about 1:1 toabout 1:20.

Embodiment 5 comprises the nanocomposite of any one of embodiments 1 to4, wherein the nanoparticles of the PbOx have a Pb:O atomic ratio about1:1 to about 1:2.

Embodiment 6 comprises the nanocomposite of any one of embodiments 1 to5, wherein the Pb and the PbOx are present in the nanocomposite in arespective molar ratio of about 1:0.1 to about 0.1:1.

Embodiment 7 comprises the nanocomposite of any one of embodiments 1 to6, wherein PbOx is present on the surface of at least some of the Pbnanoparticles forming a shell on core nanoparticle morphology.

Embodiment 8 comprises the nanocomposite of any one of embodiments 1 to7, further comprising at least one additional element selected from thegroup consisting of a transition metal, Al, Si, P, Sn, Sb, and Bi.

Embodiment 9 comprises the nanocomposite of embodiment 8, wherein the atleast one additional element is (a) incorporated within thenanoparticles of Pb, (b) incorporated as an oxide within thenanoparticles of PbOx, (c) dispersed within the carbon nanoparticlematrix as elemental nanoparticles, (d) dispersed within the carbonnanoparticle matrix as oxide nanoparticles, or (e) a combination of twoor more of (a), (b), (c), and (d).

Embodiment 10 comprises the nanocomposite of embodiment 8 or 9, whereinthe at least one additional element is selected from the groupconsisting of Mn, Ni, Fe, Sb, and Sn.

Embodiment 11 comprises the nanocomposite of any one of embodiments 8 to10, wherein the at least one additional element comprises a combinationof Sb and Sn, or a combination of Sb and Ni.

Embodiment 12 comprises the nanocomposite of any one of embodiments 8 to11, wherein the at least one additional element is present in thenanocomposite at a concentration of about 50% to about 100% expressed asa percentage of the Pb in the nanocomposite.

Embodiment 13 comprises a method of preparing the nanocomposite of anyone of embodiments 1 to 12 comprising grinding a mixture comprising alead oxide material and a carbon material together in a high-energy ballmill under an inert atmosphere until a homogeneous dispersion of thenanoparticles of Pb and PbOx is formed within the carbon nanoparticlematrix.

Embodiment 14 comprises the method of embodiment 13, wherein the mixtureof the lead oxide material and the carbon material further comprises oneor more additional material comprising at least one additional elementselected from the group consisting of a transition metal, Al, Si, P, Sn,Sb, and Bi.

Embodiment 15 comprises the method of embodiment 13 or 14, wherein thelead oxide material and the carbon material are initially present in theball mill in a respective weight ratio of about 9:1 to about 1:1.

Embodiment 16 is an electrode for a lithium-ion or sodium-ion batterycomprising the nanocomposite of any one of embodiments 1 to 12 coated ona conductive current collector with a binder.

Embodiment 17 comprises the electrode of embodiment 16, wherein thenanocomposite is coated on the conductive current collector at a loadingof about 0.2 to about 1 g/m² (e.g., about 0.33 g/m²).

Embodiment 18 is an electrochemical cell comprising a first electrodecomprising a lead-lead oxide-carbon nanocomposite, a second electrode,an ion-conductive separator between the first electrode and the secondelectrode, and an electrolyte comprising a lithium salt or a sodium saltin a non-aqueous solvent at a concentration of about 0.1 to about 5 Mcontacting the first electrode, the second electrode, and the separatorcontacting the first electrode, the second electrode, and the separator,wherein the first electrode is the electrode of embodiment 16 or 17.

Embodiment 19 comprises the electrochemical cell of embodiment 18,wherein the electrolyte further comprises 1-fluoroethylene carbonate ata concentration of about 1 wt % to about 50 wt %.

Embodiment 20 is a battery comprising a plurality of the electrochemicalcells of embodiment 18 or 19 electrically connected in series, inparallel, or in both series and parallel.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows X-ray diffraction (XRD) patterns for a Pb—O—C compositematerials; Panel (a) shows XRD patterns for nanocomposites made frommade from (a) PbO (top spectrum) and Pb₃O₄ (bottom spectrum) as the leadoxide source for the ball milling process; Panel (b) shows the effectsof milling time for a nanocomposites formed from PbO as the lead oxidesource; the positions of peaks corresponding to metallic Pb and PbOphases are marked with dots and asterisks, respectively.

FIG. 2A shows a transmission electron microscopy (TEM) image of Pb andPbOx nanoparticles (darker regions) uniformly embedded in the matrix ofcarbon nanoparticles (surrounding lighter background).

FIG. 2B shows (A) the XRD patterns of the shell on core PbOx@Pbnanoparticle over time wherein the Pb, post high-energy ball milling, isreacted with oxygen in the atmosphere to form the PbOx shell; and (B)the X-ray Photoelectron Spectroscopy (XPS) spectrum of the shell on corePbOx@Pb nanoparticle (a) before ion-gun sputtering and (b) after ion-gunsputtering for two minutes.

FIG. 3 shows electrochemical evaluations of a Pb—O—C nanocomposite in asodium cell including (A) plots of initial voltage profiles (voltageversus specific capacity for the first three cycles); and (B) plots ofspecific capacity versus cycle number.

FIG. 4 shows electrochemical evaluations of a Pb—O—C nanocomposite in asodium cell including (A) plots of initial voltage profiles (voltageversus specific capacity for the first two cycles); and (B) plots ofspecific capacity versus cycle number.

FIG. 5 shows X-ray diffraction (XRD) patterns for a Pb—O—C nanocompositematerials prepared by grinding a mixture of PbOx, carbon, and a materialcontaining an additional element (Mn₂O₃, NiO, Fe₂O₃, Sb, SnO, and Sn) ina high-energy ball mill (i.e., Pb_(y)M_(1−y)-O—C nanocomposites),compared to a Pb—O—C nanocomposite material prepared from PbOx andcarbon, alone, with no additional element included.

FIG. 6 shows X-ray diffraction (XRD) patterns for a Pb—O—C nanocompositematerials prepared by grinding a mixture of PbOx, carbon, and a materialcontaining two additional elements (SbNi and SnSb) in a high-energy ballmill, compared to a Pb—O—C nanocomposite material prepared from PbOx andcarbon, alone, with no additional elements included.

FIG. 7 shows initial discharge capacities, first charge capacities, andsecond discharge capacity (mAh/g) for the nanocomposites of FIG. 5 issodium (SIB) and lithium (LIB) cells.

FIG. 8 A shows initial discharge capacities, first charge capacities,and second discharge capacity (mAh/g) for the nanocomposites of FIG. 6in sodium (SIB) and lithium (LIB) cells.

FIG. 8B shows plots of discharge capacities versus the number of cycles,normalized initially to 100%, for sodium cells comprising thenanocomposites represented in FIG. 6 .

FIG. 9 depicts a schematic representation of an electrochemical cell.

FIG. 10 depicts a schematic representation of a battery consisting of aplurality of cells connected electrically in series and in parallel.

DETAILED DESCRIPTION

The Pb—O—C nanocomposite materials described herein are prepared by ahigh-energy ball milling process, which imparts unique structural andcompositional properties to the resulting nanocomposite materials.High-energy ball milling induces chemical as well as physical changes tothe milling mixture of PbOx and carbon. In particular, the PbOx andcarbon undergo redox reactions where some carbon is oxidized and somePbOx is reduced to elemental Pb. At the same time, grinding of theinitial PbOx and carbon powders in the high-energy ball mill reduces theparticle size of the powders, intimately mixes the materials. The redoxreactions result in the Pb and any remaining PbOx being embedded in amatrix of carbon nanoparticles. When an additional element or a compound(e.g., an oxide, a salt, an alloy, etc.) containing one or moreadditional elements is included in the mixture of PbOx and carbon, theother element can also undergo reactions with the carbon and the PbOx toincorporate the additional element or elements (M) into the resultingnanocomposite (e.g., as oxide nanoparticles, elemental nanoparticles,mixed PbM oxide nanoparticles, PbM alloys nanoparticles, and the like).The nanocomposites are useful as electrode active materials forelectrodes (e.g., anodes) in lithium-ion and sodium-ion secondaryelectrochemical cells and batteries.

Typically, the carbon material utilized in the ball milling process is aform of carbon black. Alternatively, other forms of carbon such as hardcarbon, graphite or activated carbon can be used. The carbon, inpowdered form, is mixed with one or more form of PbOx, such as PbO,PbO₂, and Pb₃O₄ in a weight ratio of PbOx to carbon of about 5:5 toabout 9:1, preferably about 6:4 to about 8:2 (e.g., about 7:3). Powdersare loaded into ball mill at room temperature under an inert gas (e.g.,Ar), and then ball milled with no externally provided heating for about1 to about 12 hours, preferably about 3 to about 9 hours.

The high-energy milling generally results in a product withnanoparticles of Pb and nanoparticles of a PbOx homogeneously dispersedin a carbon nanoparticle matrix. The nanoparticles of Pb typically havea mean diameter of about 2 to about 20 nm; the nanoparticles of the PbOxtypically have a mean diameter of about 2 to about 20 nm; and the carbonnanoparticles typically have a particle size of about 10 to about 200nm, as determined by electron microscopy. The nanocomposite has a Pb:Celemental ratio of about 1:1 to about 1:20; and the nanoparticles of thePbOx typically have a Pb:O atomic ratio of about 1:1 to about 1:2 (e.g.,about 1:1). The Pb and the PbOx are typically present in thenanocomposite in a respective molar ratio of about 9:1 to about 1:1.

When it is desired to include one or more elements, M, other than Pb, Oor C (e.g., M=Al, Si, P, Sn, Sb, Bi, and/or transition metal such as Ni)into the nanocomposite, an additional material comprising M is includedin the mixture of PbOx and C prior to high-energy ball milling. Thematerial that includes the additional element generally is included inthe mixture for grinding at a concentration of about 25% to about 50%expressed as a percentage of the Pb in the nanocomposite.

High-energy ball milling has been known since at least the late 1960'sand has been described as a process in which a powder mixture issubjected to high-energy collisions from the balls inside of a sealedcontainer. The container, which contains a sample and one or more balls,is shaken in a complex motion that combines back-and-forth swings,lateral movements, with high frequency, low amplitude vibrations, andsometimes also describing a figure-8 motion. Strong G-forces develop inthe container due to both the motion of the container, and the motionsof the grinding ball in the container with the material to be ground.High-energy ball milling can reduce even very hard materials to veryfine particles, and even to nano-sized particles for some materials. Infact, the energy input into the materials being ground is high enough toinduce chemical reactions within some materials. Because of this, theprocess is generally performed under an inert atmosphere. High-energyball milling has been used to form alloys between various metals andother materials, and accordingly is sometimes referred to as mechanicalalloying. In the case of the carbon and PbOx materials described herein,the energy imparted to the materials during the grinding process inducesredox reactions between the carbon, the PbOx and any other materialsthat are present during the grinding process.

Equipment for high-energy ball milling also is well known, such as theRETSCH EMAX and PM 400 mills, and the SPEX model 8000 shaker mill. Highenergy ball milling and equipment therefor are described in Yadof, etal. Nanoscience and Nanotechnology, 2012; 2(3): 22-48, which isincorporated herein by reference in its entirety.

In electrochemical cell and battery embodiments described herein, theelectrolyte comprises an electrolyte salt (e.g., an electrochemicallystable lithium salt or a sodium salt) dissolved in a non-aqueoussolvent. Any lithium electrolyte salt can be utilized in the electrolytecompositions for lithium electrochemical cells and batteries describedherein, such as the salts described in Jow et al. (Eds.), Electrolytesfor Lithium and Lithium-ion Batteries; Chapter 1, pp. 1-92; Springer;New York, N.Y. (2014), which is incorporated herein by reference in itsentirety.

Non-limiting examples of lithium salts include, e.g., lithiumbis(trifluoromethanesulfonyl)imidate (LiTFSI), lithium2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium trifluoromethanesulfonate(LiTf), lithium perchlorate (LiClO₄), lithium bis(oxalato)borate(LiB(C₂O₄)₂ or “LiBOB”), lithium difluoro(oxalato)borate (LiF₂BC₂O₄ or“LiDFOB”), lithium tetrafluoroborate (LiBF₄), lithiumhexafluorophosphate (LiPF₆), lithium hexafluoroarsenate (LiAsF₆),lithium thiocyanate (LiSCN), lithium bis(fluorosulfonyl)imidate (LiFSI),lithium bis(pentafluoroethylsulfonyl)imidate (LiBETI), lithiumtetracyanoborate (LiB(CN)₄), lithium nitrate, combinations of two ormore thereof, and the like. The lithium salt can be present in theelectrolyte solvent at any concentration suitable for lithium batteryapplications, which concentrations are well known in the secondarybattery art. As used herein the term “lithium battery” refers toelectrochemical cells and combinations of electrochemical cells in whichlithium (e.g., lithium ion) shuttles between an anode and a cathode, andincludes so-called full cells with an anode material (e.g., graphite)that can accommodate intercalated lithium ions, as well as so-calledhalf-cells in which the anode is lithium metal. In some embodiments, thelithium salt is present in the electrolyte at a concentration in therange of about 0.1 M to about 5 M, e.g., about 0.5 M to 2 M, or 1 M to1.5M. A preferred lithium salt is LiPF₆.

For sodium electrolytes, sodium salts of the same anions as the lithiumelectrolyte salts described above can be utilized, such as, e.g., sodiumbis(trifluoromethanesulfonyl)imidate (NaTFSI), sodium2-trifluoromethyl-4,5-dicyanoimidazolate (NaTDI), sodium4,5-dicyano-1,2,3-triazolate, sodium trifluoromethanesulfonate, sodiumperchlorate, sodium bis(oxalato)borate, sodium difluoro(oxalato)borate,sodium tetrafluoroborate (NaBF₄), sodium hexafluorophosphate (NaPF₆),sodium hexafluoroarsenate, sodium thiocyanate (NaSCN), sodiumbis(fluorosulfonyl)imidate (NaFSI), sodiumbis(pentafluoroethylsulfonyl)imidate), sodium tetracyanoborate, sodiumnitrate, combinations of two or more thereof, and the like.

The non-aqueous solvent for the electrolyte compositions include thesolvents described in Jow et al. (Eds.), Electrolytes for Lithium andLithium-ion Batteries; Chapter 2, pp. 93-166; Springer; New York, N.Y.(2014), which is incorporated herein by reference in its entirety.Non-limiting examples of solvents for use in the electrolytes include,e.g., an ether, a carbonate ester (e.g., a dialkyl carbonate or a cyclicalkylene carbonate), a nitrile, a sulfoxide, a sulfone, afluoro-substituted linear dialkyl carbonate, a fluoro-substituted cyclicalkylene carbonate, a fluoro-substituted sulfolane, and afluoro-substituted sulfone. For example, the solvent can comprise anether (e.g., glyme or diglyme), a linear dialkyl carbonate (e.g.,dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methylcarbonate (EMC) and the like), a cyclic alkylene carbonate (ethylenecarbonate (EC), propylene carbonate (PC) and the like), a sulfolane(e.g., sulfolane or an alkyl-substituted sulfolane), a sulfone (e.g., adialkyl sulfone such as a methyl ethyl sulfone), a fluoro-substitutedlinear dialkyl carbonate, a fluoro-substituted cyclic alkylenecarbonate, a fluoro-substituted sulfolane, and a fluoro-substitutedsulfone. The solvent can comprise a single solvent compound or a mixtureof two or more solvent compounds.

In some embodiments, the non-aqueous solvent for a lithiumelectrochemical cell as described herein can be an ionic liquid. Anyelectrochemically stable ionic liquid solvent can be utilized in theelectrolytes described herein, such as the solvents described in Jow etal. (Eds.), Electrolytes for Lithium and Lithium-ion Batteries; Chapter4, pp. 209-226; Springer; New York, N.Y. (2014), which is incorporatedherein by reference in its entirety. In the case of lithiumelectrochemical cells and batteries, the ionic liquid can optionallyinclude a lithium cation, and can act directly as the electrolyte salt.Similarly, in the case of sodium electrochemical cells and batteries,the ionic liquid can optionally include a sodium cation, and can actdirectly as the electrolyte salt.

The electrolyte compositions for lithium and sodium electrochemicalcells and batteries described herein also can optionally comprise anadditive such as those described in Jow et al. (Eds.), Electrolytes forLithium and Lithium-ion Batteries; Chapter 3, pp. 167-182; Springer; NewYork, N.Y. (2014), which is incorporated herein by reference in itsentirety. Such additives can provide, e.g., benefits such as SEI,cathode protection, electrolyte salt stabilization, thermal stability,safety enhancement, overpotential protection, corrosion inhibition, andthe like. The additive can be present in the electrolyte at anyconcentration, but in some embodiments is present at a concentration inthe range of about 0.0001 M to about 0.5 M. In some embodiments, theadditive is present in the electrolyte at a concentration in the rangeof about 0.001 M to about 0.25 M, or about 0.01 M to about 0.1 M. Apreferred additive is 1-fluoroethylene carbonate (FEC), which preferablyis included in the electrolyte at a concentration of about 1 to 50 wt %,more preferably about 2 to 20 wt %.

The nanocomposites described herein are useful as electrode activematerials for in a lithium-ion or sodium-ion electrochemical cell. Suchcells typically comprise a positive electrode (cathode), a negativeelectrode (anode) comprising the Pb—O—C nanocomposite as an anode activematerial (optionally in combination with a carbon material), and aporous separator between the cathode and anode, with the electrolyte incontact with both the anode and cathode, as is well known in the batteryart. A battery can be formed by electrically connecting two or more suchelectrochemical cells in series, parallel, or a combination of seriesand parallel. The electrodes described herein preferably are utilized asthe anode in a full-cell configuration in lithium-ion and sodium-ioncells and batteries. Electrochemical cells and battery designs andconfigurations, anode and cathode materials, as well as electrolytesalts, solvents and other battery or electrode components (e.g.,separator membranes, current collectors), which can be used in theelectrolytes, cells and batteries described herein, are well known inthe secondary battery art, e.g., as described in “Lithium BatteriesScience and Technology” Gholam-Abbas Nazri and Gianfranco Pistoia, Eds.,Springer Science+Business Media, LLC; New York, N.Y. (2009), which isincorporated herein by reference in its entirety.

Processes used for manufacturing lithium and sodium cells and batteriesare well known in the art. The active electrode materials are coated onboth sides of metal foil current collectors (typically copper for theanode and aluminum for the cathode) with suitable binders such aspolyvinylidene difluoride and the like to aid in adhering the activematerials to the current collectors. In the cells and batteriesdescribed herein, the anode active material is a Pb—O—C nanocompositematerial described herein, which optionally can be utilized with aseparate carbon material such as graphite, and the cathode activematerial typically is a lithium metal oxide material (for lithium cellsand batteries) or a sodium metal oxide material (for sodium cells andbatteries). Cell assembly typically is carried out on automatedequipment. The first stage in the assembly process is to sandwich aseparator between the anode. The cells can be constructed in a stackedstructure for use in prismatic cells, or a spiral wound structure foruse in cylindrical cells. The electrodes are connected to terminals andthe resulting sub-assembly is inserted into a casing, which is thensealed, leaving an opening for filling the electrolyte into the cell.Next, the cell is filled with the electrolyte and sealed undermoisture-free conditions.

Once the cell assembly is completed the cell typically is subjected toat least one controlled charge/discharge cycle to activate the electrodematerials and in some cases form a solid electrolyte interface (SEI)layer on the anode. This is known as formation cycling. The formationcycling process is well known in the battery art and involves initiallycharging with a low voltage (e.g., substantially lower that thefull-cell voltage) and gradually building up the voltage. The SEI actsas a passivating layer which is essential for moderating the chargingprocess under normal use. The formation cycling can be carried out, forexample, according to the procedure described in Long et al. J.Electrochem. Soc., 2016; 163 (14): A2999-A3009, which is incorporatedherein by reference in its entirety. This procedure involves a 1.5 V tapcharge for 15 minutes at C/3 current limit, followed by a 6-hour restperiod, and then 4 cycles at C/10 current limit, with a current cutoff(i≤0.05 C) at the top of each charge.

Electrodes comprising the Pb—O—C nanocomposite described herein, can beutilized with any combination of cathode and electrolyte in any type ofrechargeable battery system that utilizes a non-aqueous electrolyte. Insome lithium battery embodiments, the cathode active material cancomprise a layered lithium metal oxide cathode material such as LiMO₂wherein M=Mn, Ni, Co or a combination thereof (e.g., a layered lithiumnickel-manganese-cobalt oxide such as LiNi_(0.5)Mn_(0.3)CO_(0.2)O₂ (alsoknown as “NMC532”), LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂ (also known as“NMC622”), and similar materials). In other embodiments, the cathode cancomprise a spinel lithium metal oxide such as LiM′₂O₄ wherein M′=Mn, Ni,Co or a combination thereof, a structurally integrated ‘layered-layered’(LL) lithium metal oxide such as xLi₂MnO₃.(1−x)LiMn_(y)M_(1−y)O₂ wherein0<x<1, 0≤y≤1, M=Ni, Co, or Ni and Co; a structurally integrated‘layered-spinel’ (LS) lithium metal oxide such asxLi₂MnO₃.(1−x)Li₂Mn_(y)M_(2−y)O₄ wherein 0<x<1, 0≤y≤2, M=Ni, Co, or Niand Co; a structurally integrated ‘layered-layered-spinel’ (LLS) lithiummetal oxide such as z[xLi₂MnO₃.Li₂Mn_(y)M_(2−y)O₄].(1−z)Li₂M′₂O₄ wherein0<x<1, 0≤y≤1, 0<z<1, M=Ni, Co, or Ni and Co, and M′=Mn, Ni, Co or acombination thereof (e.g.,0.85[0.25Li₂MnO₃.(0.75)LiMn_(0.375)Ni_(0.375)Co_(0.25)O₂].0.15LiM′₂O₄wherein M′=a combination Mn, Ni, and Co); or any other cathode activematerial used in lithium-ion batteries.

In some sodium battery embodiments, the cathode active can be sodiummetal oxide materials such as layered transition metal oxides (e.g.,NaMO₂ (M=Co, Mn), Na_(0.67)Fe_(0.5)Mn_(0.5)O₂,Na_(0.76)Fe_(0.1)Mn_(0.5)Ni_(0.3)Mg_(0.1)O₂,NaNi_(0.45−x)Mn_(0.25)Ti_(0.3)Co_(x)O₂ (0<x<0.45) and similarmaterials), sodium metal phosphates such as NaMPO₄ (M=Mn, Fe), Na_(x)V_(1−y)M_(y)(PO₄)₃ (M=Mn, Fe, Ni), Na₃V₂O_(2x)(PO₄)₂F_(3−2x)(0≤x≤1), andNa₂FeP₂O₇. Some useful cathode materials for sodium batteries aredescribed in Mukherjee et al., Materials, 2019: 12, 1952 (pages 1-52),which is incorporated herein by reference in its entirety.

As used herein, a structurally-integrated composite metal oxide is amaterial that includes domains (e.g., locally ordered, nano-sized ormicro-sized domains) indicative of different metal oxide compositionshaving different crystalline forms (e.g., layered or spinel forms)within a single particle of the composite metal oxide, in which thedomains share substantially the same oxygen lattice and differ from eachother by the elemental and spatial distribution of metal ions in theoverall metal oxide structure. Structurally-integrated composite metaloxides are different from and generally have different properties thanmere mixtures of two or more metal oxide components (for example, meremixtures do not share a common oxygen lattice).

Positive electrodes typically are formed by combining a powdered mixtureof the active material and some form of carbon (e.g., carbon black,graphite, or activated carbon) with a binder such as (polyvinylidenedifluoride (PVDF), carboxymethylcellulose, and the like) in a solvent(e.g., N-methylpyrrolidone (NMP) or water) and the resulting mixture iscoated on a conductive current collector (e.g., aluminum foil) and driedto remove solvent and form an active layer on the current collector.

The negative electrodes also typically will include some form of carbon(e.g., carbon black, graphite, or activated carbon) in combination withthe Pb—O—C nanocomposite materials described herein. The carbon is mixedwith the active nanocomposite and a binder such as (polyvinylidenedifluoride (PVDF), carboxymethyl cellulose, and the like) in a solvent(e.g., NMP or water) and the resulting mixture is coated on a conductivecurrent collector (e.g., copper foil) and dried to remove solvent andform an active layer on the current collector.

The following non-limiting Examples are provided to illustrate certainfeatures of the compositions and methods described herein.

Example 1. Preparation of Pb—O—C Nanocomposites

A series of Pb—O—C nanocomposites were synthesized using a high-energySPEX ball mill. Mixtures of PbO and carbon black (SUPER P) or Pb₃O₄ andcarbon black (SUPER P) in 7:3 PbOx:C weight ratios (about 4 grams persample) were sealed in a stainless steel jar (35 mL) containing about 40grams of stainless steel balls (¼ inch in diameter) under an inertatmosphere (Ar), and were shaken in a high-energy SPEX 8000M ball millfor 6 hours (h) at 1060 cpm (cycle per minute). The jars were loaded atroom temperature, however some heating occurs naturally during the ballmilling.

FIG. 1 shows X-ray diffraction patterns for Pb—O—C composite materialssynthesized by the above described synthesis method. Panel (a) showsX-ray diffraction patterns for nanocomposites made from PbO (topspectrum) and Pb₃O₄ (bottom spectrum) as the lead oxide source for theball milling process. Panel (b) shows the effects of milling time fornanocomposites formed from PbO as the lead oxide source. The positionsof peaks corresponding to metallic Pb and PbO phases are marked withdots and asterisks, respectively. The carbon phase is also evident asbroad background hump in the 2-theta (20) range between about 25 and 30degrees. The metallic Pb phase is formed by a reduction reaction of thePbOx starting material and carbon precursor materials during thehigh-energy ball milling process. PbO and Pb₃O₄ starting materialsproduce different ratios of PbOx to metallic Pb in the nanocomposites.As ball milling time increases, the fractional amounts of metallic Pbincreases. Nanoparticle aggregation also increases with milling time.

The morphology of Pb—O—C composite samples have been analyzed bytransmission electron microscopy (TEM). FIG. 2A shows a TEM image of Pband PbOx nanoparticles (darker regions) uniformly embedded in the matrixof carbon nanoparticles (lighter surrounding background). This uniquenanoscale composite morphology is advantageous in dissipatingelectrochemically-induced strain during the reversible alloying andconversion reactions of Pb and PbOx with Li or Na in a lithium or sodiumcell during charging and discharging. The nanocarbon matrix can also actas a deformation buffer for the large volume expansion of Pb and PbOxactive materials during charging and discharging, thus maintaining theelectrical connectivity of the particles. Energy-dispersive X-rayspectroscopy (EDS) mapping was used to confirm the distribution of Pb,O, and C within the nanocomposite.

The Pb nanoparticles can react with air to oxidize the particle surfaceand this process can be accelerated by heating the powder or anelectrode laminate in air. The oxidation of the surface of thenanoparticles results in an exterior shell of PbOx. The presence of thePbOx is observed in the XRD pattern (stars markers) given in FIG. 2B,Panel A in which the growing diffraction peaks arise from increasingPbOx in the sample. Since this oxidation of the Pb nanoparticles to PbOxis self-limiting, we refer to this configuration as core Pb with shellof PbOx on the surface or PbOx@Pb.

The example of shell on core PbOx@Pb is further demonstrated in FIG. 2B,Panel B in which the X-ray Photoelectron Spectroscopy which wasconducted on the sample is shown. Importantly, the Pb oxide shifted Pb 4f signal is present at the beginning indicating the presence of oxideexterior shell, then, as the sputtering of the surface is conducted(upper data), then the Pb 4 f signal from PbOx disappears and that ofmetallic Pb is maximally present thus indicating, again, a self-limitedshell of PbOx on the surfaces.

Example 2. Electrochemical Evaluation of Pb—O—C Nanocomposites inLithium and Sodium Cells

Electrodes were prepared from the nanocomposite samples of Example 1 andcommercial PbO and Pb₃O₄ by combining the Active material, i.e., Pb—O—Cnanocomposite or commercial PbOx (as comparison examples) with SUPER-Pcarbon black and PVDF binder in the weight ratios of Active:C:PVDF shownin Table 1, and coating the resulting mixtures on a Cu current collectorat a coating level of about 300 g/m², followed by drying at 75° C., for12 hours. Another comparison electrode was prepared without any (seelast entry in Table 1).

TABLE 1 Active Compound Electrode Laminate Pb—O—C #1 (from PbO)Active:Carbon:PVDF = 8:1:1 (w/w/w) Pb—O—C #2 (from Pb₃O₄)Active:Carbon:PVDF = 8:1:1 (w/w/w) Commercial PbO Active:Carbon:PVDF =7:2:1 (w/w/w) Commercial Pb₃O₄ Active:Carbon:PVDF = 7:2:1 (w/w/w)SUPER-P Carbon Black Carbon:PVDF = 9:1 (w/w)

A nanocomposite from Example 1 (Pb—O—C #1) was cycle tested in a lithiumhalf-cell with Li metal as counter electrode (CE) and the Pb—O—Cnanocomposite electrode as the working electrode (WE). The electrolytesused in these evaluations were a solutions of 1.2 M LiPF₆ dissolved in amixture solvent of ethylene carbonate (EC) and ethyl methyl carbonate(EMC), with or without about 10 wt % FEC as an additive. The initialcharge-discharge curves for a Pb—O—C nanocomposite prepared from PbO asthe PbOx starting material is shown in FIG. 3 , Panel A for the cellutilizing the electrolyte without FEC. The cycling performance for thesame nanocomposite is shown in FIG. 3 , Panel B, with and without FECadditive, compared with conventional PbO-based and Pb₃O₄-basedelectrodes. The cycling performance of the nanocomposite (about 430mAh/g) was far superior to the conventional electrodes (less than 50mAh/g steady state discharge capacity). Addition of FEC provides asignificant increase in the steady state cycling performance, leading toa gravimetric capacity of about 500 mAh/g.

A nanocomposite Pb—O—C #1 from Example 1 also was cycle tested in asodium half-cell with Na metal as counter electrode (CE) and thePb/Pb-oxide/C nanocomposite electrode as the working electrode (WE). Theelectrolyte was a solution of 1M NaPF₆ dissolved in a mixture solvent ofEC and diethyl carbonate (DEC) with 2 wt % FEC as an additive. Theinitial charge-discharge curves for a Pb—O—C nanocomposite prepared fromPbO as the PbOx starting material is shown in FIG. 4 , Panel A. Thecycling performance for the same nanocomposite is shown in FIG. 4 ,Panel B, compared with conventional PbO-based and Pb₃O₄-basedelectrodes. The cycling performance of the nanocomposite, with a steadystate specific discharge capacity between 200 and 240 mAh/g, which issurprisingly far superior to the conventional electrodes (about 50 mAh/gsteady state discharge capacity). Because of the high mass per volumedensity of the Pb—O—C nanocomposite, this electrode provided about 1600mAh/cm³ volumetric energy density, which is greater than the volumetricenergy density of graphite (600 mAh/cm³ in a lithium cell), andapproaches the volumetric energy density of Si (2200 mAh/cm³ in alithium cell). It is believed that pre-sodiation of the Pb—O—Cnanocomposite could ameliorate the observed first cycle irreversiblecapacity loss (ICL) of approximately 43%.

Example 3. Preparation of Pb_(y)M_((1−y))-O—C Nanocomposites

Pb_(y)M_((1−y))-O—C (0<y<1) nanocomposite materials containing one ortwo additional elements were prepared by grinding a mixture of PbOx,carbon, and either a material containing a single additional element(Mn₂O₃, NiO, Fe₂O₃, Sb, SnO, or Sn), or a material containing twoadditional elements (SbNi or SnSb). Lead oxide (PbO) and a metal oxidecontaining a single additional element (MOx) (7:3 Pb:M molar ratio) weremixed with carbon black in a 7:3 weight ratio of the Pb/M oxides tocarbon (about 4 g per sample) in stainless steel jars 35 mL filled underan inert atmosphere (Ar) and shaken in a high-energy ball mill for 6 hat 1060 cpm.

Similarly, mixtures of lead oxide (PbO) and oxides of two additionalelements (M and M′) having the molar ratio of 2:1:1 (Pb:M:M′) were mixedwith carbon black in a 7:3 (PbMM′Ox:C) weight ratio (about 4 g persample) in 35 mL stainless steel jars filled under an inert Aratmosphere and shaken in a high-energy ball mill for 6 h at 1060 cpm.

FIG. 5 shows X-ray diffraction (XRD) patterns for thePb_(y)M_((1−y))-O—C nanocomposite materials containing one additionalelement described above, compared to a Pb—O—C nanocomposite materialprepared from PbOx and carbon, alone. The spectra in FIG. 5 show thatthe additional materials react well with the PbOx material forming thePbM alloy phase and PbMOx compounds.

FIG. 6 shows X-ray diffraction (XRD) patterns for thePb_(y)M_((1−y))-O—C nanocomposite materials containing two additionalelements (Sb—Ni or Sn—Sb) described above, compared to a Pb—O—Cnanocomposite material prepared from PbOx and carbon, alone. The spectrain FIG. 6 show that the two additional elements react well with the PbOxmaterial forming a PbMM′ alloy phase and PbMM′Ox compounds.

Example 4. Electrochemical Evaluation of Pb_(y)M_((1−y))-O—CNanocomposites in Lithium and Sodium Cells

Electrodes were prepared from the Pb_(y)M_((1−y))-O—C nanocompositesamples of Example 3 by combining the nanocomposite with SUPER-P carbonblack and PVDF binder in the weight ratios of nanocomposite:C:PVDF of8:1:2, and coating the resulting mixtures on a Cu current collector at acoating level of about 300 g/m², followed by drying at 75° C., for 12hours.

The electrodes were evaluated in lithium and sodium half-cells cycled atroom temperature in the voltage range between 0.005-3.0 V vs Li and0.005-2.0 vs Na, respectively. The applied current density was 100 mA/g.The electrolytes used in these evaluations were solutions of 1.2 M LiPF₆in EC/EMC (3:7 weigh ratio) with 10 wt % FEC for Li cells and 1 M NaPF₆in EC/DEC (1:1 volume ratio) with 2 wt % FEC for sodium cells.

FIG. 7 shows initial specific capacity (mAh/g), and capacities for thesubsequent cycle for the nanocomposites of FIG. 5 in sodium (SIB) andlithium (LIB) cells. The results in FIG. 7 show improved specificcapacity and decreased initial irreversibility with the addition of asecond element to the PbOx nanocomposite.

FIG. 8A shows initial specific capacity (mAh/g), and capacities for thesubsequent cycle for the nanocomposites of FIG. 6 . The results in FIG.8A show comparison between Pb—O—C with PbMM′-O—C in Li cells (LIB) andNa cells (SIB). Cycling performance can be expected to be better frombuffering effect of additional materials, even if capacity in Na cellwas slightly decreased due to inactive elements. Capacity of Li cellsusing Pb-M-M′-O—C were increased compared to Pb—O—C.

FIG. 8B shows plots of discharge capacities versus the number of cycles,normalized initially to 100%, for sodium cells comprising thenanocomposites represented in FIG. 6 . The addition of SbSn and SbNiimproved the capacity retention significantly relative to the Pb—O—Cexample without any additional elements.

Example 5. Electrochemical Cells and Batteries

FIG. 9 schematically illustrates a cross-sectional view of anelectrochemical cell 10 comprising electrode 12, and electrode 14comprising a Pb—O—C nanocomposite as described herein, with separator 16therebetween. A sodium-containing or lithium-containing electrolyte 18,comprising a solution of a sodium or lithium salt in a non-aqueoussolvent, contacts electrodes 12 and 14 and separator 16. The electrodes,separator and electrolyte are sealed within housing 19. FIG. 10schematically illustrates a sodium-ion or lithium-ion battery comprisinga first array 20 consisting of three series-connected electrochemicalcells 10, and a second array 22 consisting of three series-connectedelectrochemical cells 10, in which first array 20 is electricallyconnected to second array 22 in parallel.

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. The terms “consisting of” and“consists of” are to be construed as closed terms, which limit anycompositions or methods to the specified components or steps,respectively, that are listed in a given claim or portion of thespecification. In addition, and because of its open nature, the term“comprising” broadly encompasses compositions and methods that “consistessentially of” or “consist of” specified components or steps, inaddition to compositions and methods that include other components orsteps beyond those listed in the given claim or portion of thespecification. Recitation of ranges of values herein are merely intendedto serve as a shorthand method of referring individually to eachseparate value falling within the range, unless otherwise indicatedherein, and each separate value is incorporated into the specificationas if it were individually recited herein. All numerical values obtainedby measurement (e.g., weight, concentration, physical dimensions,removal rates, flow rates, and the like) are not to be construed asabsolutely precise numbers, and should be considered to encompass valueswithin the known limits of the measurement techniques commonly used inthe art, regardless of whether or not the term “about” is explicitlystated. All methods described herein can be performed in any suitableorder unless otherwise indicated herein or otherwise clearlycontradicted by context. The use of any and all examples, or exemplarylanguage (e.g., “such as”) provided herein, is intended merely to betterilluminate certain aspects of the invention and does not pose alimitation on the scope of the invention unless otherwise claimed. Nolanguage in the specification should be construed as indicating anynon-claimed element as essential to the practice of the invention.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the invention unlessotherwise indicated herein or otherwise clearly contradicted by context.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:
 1. A lead-lead oxide-carbonnanocomposite comprising nanoparticles of lead (Pb) and nanoparticles ofa lead oxide homogeneously dispersed in a carbon nanoparticle matrix;wherein lead oxide is present on the surface of at least some of the Pbnanoparticles.
 2. The nanocomposite of claim 1, wherein thenanoparticles of Pb have a mean diameter in the range of about 2 toabout 20 nm as determined by electron microscopy.
 3. The nanocompositeof claim 1, wherein the nanoparticles of the lead oxide have a meandiameter in the range of about 2 to about 20 nm as determined byelectron microscopy.
 4. The nanocomposite of claim 1, wherein thenanocomposite has a elemental ratio of about 1:1 to about 1:20.
 5. Thenanocomposite of claim 1, wherein the nanoparticles of the lead oxidehave a Pb:O atomic ratio of about 1:1 to about 1:2.
 6. The nanocompositeof claim 1, wherein the Pb and the lead oxide are present in thenanocomposite in a respective molar ratio of about 1:0.1 to about 0.1:1.7. An electrode for a lithium-ion or sodium-ion battery comprising thenanocomposite of claim 1 coated on a conductive current collector with abinder.
 8. An electrochemical cell comprising a first electrodecomprising a lead-lead oxide-carbon nanocomposite, a second electrode,an ion-conductive separator between the first electrode and the secondelectrode, and an electrolyte comprising a lithium salt or a sodium saltin a non-aqueous solvent at a concentration of about 0.1 to about 5 M,wherein the electrolyte contacts the first electrode, the secondelectrode, and the separator, and wherein the first electrode is theelectrode of claim
 7. 9. The electrochemical cell of claim 8, whereinthe electrolyte further comprises 1-fluoroethylene carbonate at aconcentration of about 1 wt % to about 50 wt %.
 10. A secondary batterycomprising a plurality of the electrochemical cells of claim 8electrically connected in series, in parallel, or in both series andparallel.
 11. A lead-lead oxide-carbon nanocomposite comprisingnanoparticles of lead (Pb) and nanoparticles of a lead oxidehomogeneously dispersed in a carbon nanoparticle matrix, and furthercomprising at least one additional element selected from the groupconsisting of a transition metal, Al, Si, P, Sn, Sb, and Bi.
 12. Thenanocomposite of claim 11, wherein the at least one additional elementis (a) incorporated within the nanoparticles of Pb, (b) incorporated asan oxide within the nanoparticles of the lead oxide, (c) dispersedwithin the carbon nanoparticle matrix as elemental nanoparticles, (d)dispersed within the carbon nanoparticle matrix as oxide nanoparticles,or (e) a combination of two or more of (a), (b), (c), and (d).
 13. Thenanocomposite of claim 11, wherein the at least one additional elementis selected from the group consisting of Mn, Ni, Fe, Sb, and Sn.
 14. Thenanocomposite of claim 11, wherein the at least one additional elementcomprises a combination of Sb and Sn, or a combination of Sb and Ni. 15.The nanocomposite of claim 11, wherein the at least one additionalelement is present in the nanocomposite at a concentration of about 50%to about 100% expressed as a percentage of the Pb in the nanocomposite.16. An electrode for a lithium-ion or sodium-ion battery comprising thenanocomposite of claim 11 coated on a conductive current collector witha binder; and the at least one additional element is (a) incorporatedwithin the nanoparticles of Pb, (b) incorporated as an oxide within thenanoparticles of the lead oxide, (c) dispersed within the carbonnanoparticle matrix as elemental nanoparticles, (d) dispersed within thecarbon nanoparticle matrix as oxide nanoparticles, or (e) a combinationof two or more of (a), (b), (c), and (d).
 17. An electrochemical cellcomprising a first electrode comprising a lead-lead oxide-carbonnanocomposite, a second electrode, an ion-conductive separator betweenthe first electrode and the second electrode, and an electrolytecomprising a lithium salt or a sodium salt in a non-aqueous solvent at aconcentration of about 0.1 to about 5 M; wherein the electrolytecontacts the first electrode, the second electrode, and the separator;and the first electrode is the electrode of claim
 16. 18. Theelectrochemical cell of claim 17, wherein the electrolyte furthercomprises 1-fluoroethylene carbonate at a concentration of about 1 wt %to about 50 wt %.
 19. A secondary battery comprising a plurality of theelectrochemical cells of claim 17 electrically connected in series, inparallel, or in both series and parallel.